WO2019208153A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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WO2019208153A1
WO2019208153A1 PCT/JP2019/015021 JP2019015021W WO2019208153A1 WO 2019208153 A1 WO2019208153 A1 WO 2019208153A1 JP 2019015021 W JP2019015021 W JP 2019015021W WO 2019208153 A1 WO2019208153 A1 WO 2019208153A1
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group
compound
carbon atoms
nonaqueous electrolyte
secondary battery
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PCT/JP2019/015021
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English (en)
Japanese (ja)
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真梨恵 中西
健二 撹上
洋平 青山
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株式会社Adeka
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Priority to JP2020516172A priority Critical patent/JPWO2019208153A1/ja
Priority to KR1020207022766A priority patent/KR20210002452A/ko
Publication of WO2019208153A1 publication Critical patent/WO2019208153A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery including a sulfur-modified organic compound in a positive electrode and an alkali metal in a negative electrode.
  • Non-aqueous electrolyte secondary batteries such as lithium ion secondary batteries are small and light, have high energy density, and can be repeatedly charged and discharged, so portable electronic devices such as portable personal computers, handy video cameras, and information terminals. Widely used as a power source for equipment. From the viewpoint of environmental problems, electric vehicles using nonaqueous electrolyte secondary batteries and hybrid vehicles using electric power as a part of power have been put into practical use. Therefore, in recent years, further improvements in the performance of secondary batteries have been demanded from the viewpoints of the usable time of portable electronic devices, the cruising distance of automobiles, and the safety thereof.
  • Sulfur for example, has a theoretically large electric capacity compared to a positive electrode active material such as a lithium-transition metal composite oxide, and is extremely concerned about resource reserves and costs such as transition metals. small. Further, lithium metal or an alloy containing lithium metal is lighter and has a higher energy density than a negative electrode active material for a secondary battery such as carbon intercalated with lithium ions. Therefore, a lithium-sulfur secondary battery that uses lithium metal as a negative electrode active material and a material containing sulfur as a positive electrode active material is one of the promising candidates that satisfy the above-mentioned demand.
  • an electrolytic solution containing a compound having a silyl ester group is a nonaqueous electrolyte secondary battery using a lithium transition metal composite oxide or a lithium-containing transition metal phosphate compound as a positive electrode active material and artificial graphite or the like as a negative electrode active material.
  • a non-aqueous solution using a positive electrode using a sulfur-modified organic compound as a positive electrode active material and a negative electrode using an alkali metal such as lithium or sodium as a negative electrode active material is not known (for example, Patent Documents 11 and 12).
  • a compound added to the non-aqueous electrolyte of the secondary battery (hereinafter sometimes referred to as an electrolyte additive or electrolyte additive) reacts with the initial charge / discharge, so that a solid electrolyte interface is formed on the electrode surface.
  • SEI film called
  • Patent Document 13 discloses that SEI formed by adding hypervalent iodine to a non-aqueous electrolyte suppresses lithium dendrite growth and leads to improved cycle characteristics.
  • Patent Documents 14 and 15 disclose that charging-discharging efficiency and utilization efficiency of sulfur can be improved by adding LiNO 3 to a non-aqueous electrolyte.
  • An object of the present invention is to provide a positive electrode using a sulfur-modified organic compound as a positive electrode active material, which has a high capacity even after repeated charge and discharge, and has both excellent charge / discharge characteristics at low temperatures and excellent high-temperature storage stability.
  • Another object of the present invention is to provide a non-aqueous electrolyte secondary battery using a negative electrode using an alkali metal or alkaline earth metal such as lithium or sodium as a negative electrode active material.
  • the inventors of the present invention contain a compound having a specific structure when using a positive electrode containing a sulfur-modified organic compound and a negative electrode containing an alkali metal or alkaline earth metal including lithium metal. It has been found that the above problem can be achieved by using a non-aqueous electrolyte, and the present invention has been completed.
  • the present invention relates to a positive electrode containing a sulfur-modified organic compound; a negative electrode containing at least one metal selected from the group consisting of alkali metals and alkaline earth metals; and at least one compound represented by the general formula (1). And a nonaqueous electrolyte containing at least one metal salt selected from the group consisting of alkali metal salts and alkaline earth metal salts.
  • R 1 to R 3 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R 4 represents an n-valent hydrocarbon group having 1 to 10 carbon atoms, or an oxygen atom or sulfur
  • It represents an n-valent hydrocarbon group having 1 to 10 carbon atoms and containing at least one atom, and n represents an integer of 1 to 6.
  • FIG. 1 is a longitudinal sectional view schematically showing an example of the structure of a coin-type battery of the nonaqueous electrolyte secondary battery of the present invention.
  • FIG. 2 is a schematic view showing a basic configuration of a cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention.
  • FIG. 3 is a perspective view showing the internal structure of the cylindrical battery of the nonaqueous electrolyte secondary battery of the present invention as a cross section.
  • nonaqueous electrolyte secondary battery of the present invention will be described in detail based on preferred embodiments.
  • the positive electrode used for the nonaqueous electrolyte secondary battery of the present invention contains a sulfur-modified organic compound.
  • the sulfur-modified organic compound acts as a positive electrode active material.
  • the sulfur content of the sulfur-modified organic compound is not particularly limited, but is preferably 25% by mass or more, and more preferably 30% by mass or more.
  • the sulfur-modified organic compound used in the present invention is obtained by heat-treating an organic compound and sulfur.
  • the compound obtained by heat treating an organic compound and sulfur include, for example, a sulfur-modified polyacrylonitrile compound, a sulfur-modified elastomer compound, a sulfur-modified pitch compound, a sulfur-modified polynuclear aromatic ring compound, a sulfur-modified aliphatic hydrocarbon oxide, and a sulfur-modified polyether.
  • examples thereof include compounds, polythienoacene compounds, sulfur-modified polyamide compounds, and polysulfide carbon.
  • These compounds are a mixture of sulfur and polyacrylonitrile compound, elastomer compound, pitch compound, polynuclear aromatic ring compound, aliphatic hydrocarbon oxide, polyether compound, polyacene compound, polyamide compound, or hexachlorobutadiene, It can be produced by heat-denaturing at 250 to 600 ° C. in a non-oxidizing atmosphere. When these compounds are heated with sulfur, only one of these compounds may be used, or two or more may be used in combination.
  • the sulfur-modified organic compound is preferably a sulfur-modified polyacrylonitrile compound because a large charge / discharge capacity can be obtained.
  • Non-oxidizing atmosphere means an oxygen concentration of less than 5% by volume, preferably less than 2% by volume, more preferably an atmosphere substantially free of oxygen, for example, an inert gas atmosphere such as nitrogen, helium, argon, It is a sulfur gas atmosphere.
  • the sulfur-modified polyacrylonitrile compound is a compound obtained by heat-treating a polyacrylonitrile compound and elemental sulfur in a non-oxidizing atmosphere.
  • the polyacrylonitrile compound may be a homopolymer of acrylonitrile or a copolymer of acrylonitrile and other monomers.
  • the content of acrylonitrile in the copolymer of acrylonitrile and other monomers is preferably at least 90% by mass, and more preferably a polyacrylonitrile homopolymer.
  • examples of other monomers include acrylic acid, vinyl acetate, N-vinylformamide, and N, N′-methylenebis (acrylamide).
  • the temperature of the heat treatment is preferably 250 ° C. to 550 ° C.
  • the sulfur content of the sulfur-modified polyacrylonitrile is preferably 30 to 60% by mass because a large charge / discharge capacity can be obtained.
  • the sulfur-modified elastomer compound is a compound obtained by heat-treating a mixture of rubber and elemental sulfur in a non-oxidizing atmosphere.
  • the rubber include natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, and acrylonitrile butadiene rubber. These rubber
  • gum can be used individually by 1 type, and can be used in combination of 2 or more type.
  • the raw rubber may be vulcanized rubber or unvulcanized rubber.
  • the temperature of the heat treatment is preferably 250 ° C. to 550 ° C., and the sulfur content of the sulfur-modified elastomer compound is preferably 40 to 70% by mass because a large charge / discharge capacity can be obtained.
  • the sulfur-modified pitch compound is a compound obtained by heat-treating a mixture of pitches and elemental sulfur in a non-oxidizing atmosphere.
  • Pitches include petroleum pitch, coal pitch, mesophase pitch, asphalt, coal tar, coal tar pitch, organic synthetic pitch obtained by polycondensation of condensed polycyclic aromatic hydrocarbon compounds, and heteroatom-containing condensed polycyclic aroma.
  • organic synthetic pitch obtained by polycondensation of a group hydrocarbon compound.
  • Pitches are a mixture of various compounds and contain fused polycyclic aromatics.
  • the condensed polycyclic aromatic contained in the pitches may be a single species or a plurality of species. This condensed polycyclic aromatic may contain nitrogen or sulfur in addition to carbon and hydrogen in the ring.
  • the temperature of the heat treatment is preferably 300 ° C. to 500 ° C.
  • the sulfur content of the sulfur-modified pitch compound is preferably 25 to 70% by mass because a large charge / discharge capacity can be obtained.
  • Sulfur-modified polynuclear aromatic ring compounds include, for example, a mixture of benzene-based aromatic ring compounds such as naphthalene, anthracene, tetracene, pentacene, phenanthrene, chrysene, picene, pyrene, benzopyrene, perylene, coronene, and simple sulfur in a non-oxidizing atmosphere. It is a compound obtained by heat-treating.
  • aromatic ring compounds in which part of the benzene aromatic ring compound is a 5-membered ring, or hetero atom-containing heteroaromatic ring compounds in which some of these carbon atoms are replaced with sulfur, oxygen, nitrogen, etc. .
  • these polynuclear aromatic ring compounds are linear or branched alkyl groups having 1 to 12 carbon atoms, alkoxyl groups, hydroxyl groups, carboxyl groups, amino groups, aminocarbonyl groups, aminothio groups, mercaptothiocarbonylamino groups, carboxy groups. It may have a substituent such as an alkylcarbonyl group.
  • the temperature of the heat treatment is preferably 250 ° C. to 550 ° C.
  • the sulfur content of the sulfur-modified pitch compound is preferably 40 to 70% by mass because a large charge / discharge capacity can be obtained.
  • Sulfur-modified aliphatic hydrocarbon oxides are obtained by heat-treating aliphatic hydrocarbon oxides such as aliphatic alcohols, aliphatic aldehydes, aliphatic ketones, aliphatic epoxides, and fatty acids and simple sulfur in a non-oxidizing atmosphere.
  • the resulting compound The temperature of the heat treatment is preferably 300 ° C to 500 ° C.
  • the sulfur content of the sulfur-modified aliphatic hydrocarbon oxide is preferably 45 to 75% by mass because a large charge / discharge capacity can be obtained.
  • the sulfur-modified polyether compound is a compound obtained by heat-treating a polyether compound and elemental sulfur in a non-oxidizing atmosphere.
  • the polyether compound include polyethylene glycol, polypropylene glycol, ethylene oxide / propylene oxide copolymer, polytetramethylene glycol, and the like.
  • the polyether compound may be terminated with an alkyl ether group, an alkylphenyl ether group or an acyl group, or may be an ethylene oxide adduct of a polyol such as glycerin or sorbitol.
  • the temperature of the heat treatment is preferably 250 to 500 ° C.
  • the sulfur content of the sulfur-modified polyether compound is preferably 30 to 75% by mass because a large charge / discharge capacity can be obtained.
  • the polythienoacene compound is a compound having a polythienoacene structure containing sulfur represented by the following general formula (3).
  • the polythienoacene compound is a compound obtained by heat-treating an aliphatic polymer compound having a linear structure such as a polyethylene compound or a polymer compound having a thiophene structure such as polythiophene and simple sulfur in a non-oxidizing atmosphere.
  • the temperature of the heat treatment is preferably 300 ° C. to 600 ° C.
  • the sulfur content of the polythienoacene compound is preferably 30 to 80% by mass because a large charge / discharge capacity can be obtained.
  • the sulfur-modified polyamide compound is a sulfur-modified organic compound having a carbon skeleton derived from a polymer having an amide bond, specifically, an aminocarboxylic acid compound and simple sulfur, or a polyamine compound and polycarboxylic acid compound and simple sulfur, It is a compound obtained by heat treatment in a non-oxidizing atmosphere.
  • the temperature of the heat treatment is preferably 250 to 600 ° C.
  • the sulfur content of the sulfur-modified polyamide compound is preferably 40 to 70% by mass because a large charge / discharge capacity can be obtained.
  • the polysulfide carbon is a compound represented by the general formula (CS x ) n (x is 0.5 to 2, n is a number of 4 or more), for example, alkali metal sulfide such as sodium sulfide. It can be obtained by heat-treating a precursor in which a halogenated unsaturated hydrocarbon such as hexachlorobutadiene is reacted with a complex of a product and elemental sulfur.
  • the temperature of the heat treatment is preferably 300 to 450 ° C.
  • the sulfur content of the polysulfide carbon compound is preferably 65 to 75% by mass because a large charge / discharge capacity can be obtained.
  • the sulfur content can be measured by performing elemental analysis using, for example, a CHN analyzer (such as Elementer Vario MICRO cube) that can analyze sulfur and oxygen.
  • a CHN analyzer such as Elementer Vario MICRO cube
  • graphite carbon materials such as natural graphite, artificial graphite and expanded graphite, carbon materials such as carbon black, activated carbon, carbon fiber, coke, soft carbon, hard carbon, carbon nanotubes, tetramethylthiuram Vulcanization accelerators such as disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide can be used. These can be used alone or in combination of two or more.
  • the carbon material and the vulcanization accelerator can be blended in a known blending recipe at a known blending ratio.
  • the shape of the sulfur-modified organic compound is not particularly limited.
  • it is spherical, polyhedral, fibrous, rod-like, plate-like, scale-like, or amorphous, and these may be hollow.
  • a spherical or polyhedral shape is preferable.
  • the average particle diameter (D50) of the sulfur-modified organic compound is preferably 0.5 to 100 ⁇ m, more preferably 1 ⁇ m to 50 ⁇ m, and still more preferably 1 ⁇ m to 20 ⁇ m.
  • the average particle diameter (D50) refers to a 50% particle diameter measured by a laser diffraction light scattering method.
  • the particle diameter is a volume-based diameter, and the diameter of secondary particles is measured by the laser diffraction light scattering method.
  • the sulfur-modified organic compound can have a desired particle size by a method such as pulverization.
  • the pulverization may be dry pulverization performed in a gas or wet pulverization performed in a liquid such as water.
  • Examples of the industrial pulverization method include a ball mill, a roller mill, a turbo mill, a jet mill, a cyclone mill, a hammer mill, a pin mill, a rotating mill, a vibration mill, a planetary mill, an attritor, and a bead mill.
  • the positive electrode used in the present invention can be produced according to a known method.
  • the electrode mixture is applied onto the current collector by applying a mixture of the positive electrode active material, the binder and the conductive additive to the current collector by applying an electrode mixture paste slurryed with an organic solvent or water to the current collector.
  • a positive electrode on which a layer is formed can be produced.
  • binders can be used as the binder used in the present invention.
  • the binder include, for example, styrene-butadiene rubber, butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, styrene-isoprene rubber, fluorine rubber, polyethylene, polypropylene, polyamide, polyamideimide, polyimide, polyacrylonitrile, Polyurethane, polyvinylidene fluoride, polytetrafluoroethylene, styrene-acrylic acid ester copolymer, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, polyacrylate, polyvinyl alcohol, polyethylene oxide, polyvinyl pyrrolidone, polyvinyl ether, polyvinyl chloride , Polyacrylic acid, methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, Loin nanofibers, and starch.
  • an aqueous binder is preferable because it has a low environmental load and sulfur elution hardly occurs.
  • Styrene-butadiene rubber, sodium carboxymethyl cellulose, and polyacrylic acid are more preferable. Only one binder can be used, or two or more binders can be used in combination.
  • the content of the binder is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the positive electrode active material.
  • conductive assistants for electrodes can be used.
  • This conductive auxiliary agent can be mixed during the production of the sulfur-modified organic compound.
  • the particle size of the conductive aid is preferably 0.0001 ⁇ m to 100 ⁇ m, and more preferably 0.01 ⁇ m to 50 ⁇ m.
  • the content of the conductive assistant is usually 0.1 to 50 parts by mass, preferably 1 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the electrode active material.
  • Solvents for preparing the electrode mixture paste include, for example, propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propio Nitrile, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 1,3-dioxolane, nitromethane, N-methylpyrrolidone, N, N-dimethylformamide, dimethylacetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyltriamine, N, N-dimethylaminopropylamine, polyethylene oxide, tetrahydrofuran, dimethyl sulfoxide, sulfolane, ⁇ -butyrolactone, water, alcohol And the like.
  • the amount of the solvent used can be adjusted according to the method selected when coating the slurry.
  • the total amount of the sulfur-modified organic compound, the binder and the conductive auxiliary agent is 100 mass.
  • the amount is preferably 20 to 300 parts by mass, more preferably 30 to 200 parts by mass with respect to parts.
  • the electrode mixture paste composition contains, in addition to the above components, other components such as, for example, a viscosity modifier, a reinforcing material, an antioxidant, a pH adjuster, and a dispersant, as long as the effects of the present invention are not impaired. It does n’t matter.
  • known components can be used at a known blending ratio.
  • Electrode mixture paste manufacturing process In the production of the electrode mixture paste, when the positive electrode active material, the binder and the conductive additive are dispersed or dissolved in the solvent, all of them can be added to the solvent at once and dispersed, or separately added and dispersed. You can also. It is preferable to sequentially add a binder, a conductive additive, and an active material in the solvent in the order of the dispersion treatment, since these can be uniformly dispersed in the solvent. When the electrode mixture paste contains other components, the other components can be added all at once, and the dispersion treatment can be performed. However, the dispersion treatment is preferably performed every time one kind is added.
  • the dispersion treatment method is not particularly limited, but as an industrial method, for example, a normal ball mill, sand mill, bead mill, cyclone mill, pigment disperser, crushed grinder, ultrasonic disperser, homogenizer, rotation / revolution mixer, Planetary mixers, fill mixes, jet pasters, etc. can be used.
  • a conductive material such as titanium, titanium alloy, aluminum, aluminum alloy, nickel, stainless steel, nickel-plated steel, or the like is used.
  • the shape of the current collector include a foil shape, a plate shape, and a net shape, and the current collector may be either porous or non-porous.
  • these conductive materials may be subjected to surface treatment in order to improve adhesion and electrical characteristics.
  • aluminum is preferable from the viewpoint of conductivity and price, and aluminum foil is particularly preferable.
  • the thickness of the current collector is not particularly limited, but is usually 5 to 30 ⁇ m.
  • the method for applying the electrode mixture paste composition to the current collector is not particularly limited.
  • the die coater method, comma coater method, curtain coater method, spray coater method, gravure coater method, flexo coater method, knife coater method Each method such as a doctor blade method, a reverse roll method, a brush coating method, and a dip method can be used.
  • a die coater method, a knife coater method, and a doctor blade method are preferable in that a favorable surface state of the coating layer can be obtained in accordance with the viscosity and drying property of the electrode mixture paste.
  • coating to the electrical power collector of an electrode mixture paste composition can be performed to the single side
  • each side can be applied sequentially, or both sides can be applied simultaneously.
  • coat continuously on the surface of an electrical power collector can also apply
  • the thickness, length and width of the coating layer can be appropriately determined according to the size of the battery and the like.
  • the method for drying the electrode mixture paste composition applied on the current collector is not particularly limited, and a known method can be used.
  • the drying method include drying with warm air, hot air, low-humidity air, vacuum drying, drying by irradiation with far infrared rays, infrared rays, electron beams, or the like. These can be implemented in combination.
  • the temperature at the time of heating is, for example, generally about 50 ° C. to 180 ° C., but the conditions such as the temperature can be appropriately set according to the coating amount of the slurry composition, the boiling point of the solvent used, and the like. .
  • volatile components such as a solvent are volatilized from the coating film of the electrode mixture paste composition, and an electrode mixture layer is formed on the current collector.
  • the negative electrode used for the nonaqueous electrolyte secondary battery of the present invention contains at least one metal selected from the group consisting of alkali metals and alkaline earth metals. In the present invention, these metals act as a negative electrode active material.
  • Examples of the alkali metal include lithium, sodium, and potassium. These alloys can also be used as the negative electrode active material.
  • Examples of the alloy containing an alkali metal include a lithium alloy and a sodium alloy.
  • the lithium alloy is not particularly limited as long as the effect of the present invention is not hindered.
  • what added the other metal 1 mass% or less to these lithium alloys can also be used.
  • these lithium alloys those containing 30% by mass or more of lithium are preferable, and those containing 40% by mass or more are more preferable.
  • the alloy of sodium and 1 or more types of metals chosen from the group of aluminum, silicon, tin, magnesium, indium, calcium is mentioned. .
  • what added 1 mass% of other metals to these sodium alloys can also be used.
  • these sodium alloys those containing 30% by mass or more of sodium are preferable, and those containing 50% by mass or more are more preferable.
  • Examples of the alkaline earth metal include magnesium, calcium, strontium, barium and the like. These alloys can also be used as the negative electrode active material.
  • Examples of the alloy containing an alkaline earth metal include a magnesium alloy and a calcium alloy. Further, these magnesium alloys are not limited as long as the effects of the present invention are not hindered. For example, an alloy with one or more metals selected from the group of silver, indium, aluminum, nickel, germanium, silicon, and tin is used. Can be mentioned. Furthermore, what added 1 mass% or less of other metals to these magnesium alloys can also be used. Among these magnesium metals, those containing 30% by mass or more of magnesium are preferable, and those containing 40% by mass or more are more preferable.
  • the calcium alloy is not limited as long as the effects of the present invention are not hindered.
  • Examples of the calcium alloy include alloys with one or more metals selected from the group consisting of silver, indium, aluminum, nickel, germanium, silicon, and tin. Furthermore, what added 1 mass% or less of other metals to these calcium alloys can also be used. Among these calcium metals, those containing 30% by mass or more of calcium are preferable, and those containing 40% by mass or more are more preferable.
  • An alkali metal, alkaline earth metal, or an alloy containing an alkali metal or alkaline earth metal may have an inorganic protective layer or an organic protective layer on the surface, and a laminate of these may also be used. .
  • the alkali metals, alkaline earth metals, and alloys containing alkali metals or alkaline earth metals lithium and sodium are preferable, and lithium is more preferable.
  • the shape of the alkali metal, the alkaline earth metal, and the alloy containing the alkali metal or the alkaline earth metal is not particularly limited, but may be, for example, a foil shape, a plate shape, a sheet shape, or a mesh shape. Among these, a plate shape and a foil shape are preferable from the viewpoint of ease of handling.
  • the thickness is not particularly limited, but is generally 10 ⁇ m to 3 mm, preferably 50 ⁇ m to 1 mm.
  • the negative electrode current collector may not be used because the negative electrode active material itself has high electronic conductivity. However, depending on the configuration of the battery, a metal material that does not form an alloy with the negative electrode active material is used as the negative electrode current collector. You can also Although it does not specifically limit as a metal material, Stainless steel, copper, nickel, or silver is mentioned. After forming the negative electrode active material to a required size, the negative electrode can be manufactured by pressure bonding on the current collector, and after forming the negative electrode active material on the current collector, the required size is formed. You can also
  • the nonaqueous electrolyte used in the nonaqueous electrolyte secondary battery of the present invention is at least one compound selected from the group consisting of at least one compound represented by the following general formula (1) and an alkali metal salt and an alkaline earth metal salt. Contains one metal salt.
  • R 1 to R 3 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and R 4 represents an n-valent hydrocarbon group having 1 to 10 carbon atoms, or an oxygen atom or sulfur
  • It represents an n-valent hydrocarbon group having 1 to 10 carbon atoms and containing at least one atom, and n represents an integer of 1 to 6.
  • hydrocarbon group having 1 to 10 carbon atoms examples include methyl group, ethyl group, propyl group, i-propyl group, butyl group, 2-butyl group, i-butyl group, t-butyl group, pentyl group, aliphatic saturated hydrocarbon groups such as i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, nonyl, decyl; vinyl, allyl, butenyl, pentenyl Aliphatic unsaturated hydrocarbon groups such as hexenyl group and octenyl group; alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group and methylcyclohexyl group; phenyl group, methylphenyl group, ethylphenyl group, t-butylphenyl group And aromatic hydrocarbon groups such as phenyl
  • the hydrocarbon group having 1 to 10 carbon atoms is preferably a methyl group, an ethyl group, a butyl group, a vinyl group, or a phenyl group because excellent cycle characteristics and a high capacity can be obtained even after repeated charge and discharge use.
  • a methyl group is more preferred.
  • R 4 in the general formula (1) represents an n-valent hydrocarbon group having 1 to 10 carbon atoms or an n-valent hydrocarbon group having 1 to 10 carbon atoms containing at least one oxygen atom or sulfur atom.
  • N represents an integer of 1-6.
  • a compound in which R 4 is an n-valent hydrocarbon group having 1 to 10 carbon atoms is represented by n hydrogen atoms of a hydrocarbon having 1 to 10 carbon atoms.
  • R 1 to R 3 have the same meanings as in general formula (1), and * represents a binding site.
  • hydrocarbon having 1 to 10 carbon atoms examples include saturated hydrocarbons having 1 to 10 carbon atoms, unsaturated hydrocarbons having 2 to 10 carbon atoms, and aromatic hydrocarbons having 6 to 10 carbon atoms.
  • the saturated hydrocarbon having 1 to 10 carbon atoms and the unsaturated hydrocarbon having 2 to 10 carbon atoms may have a straight chain structure or a branched structure.
  • saturated hydrocarbon having 1 to 10 carbon atoms examples include methane, ethane, n-propane, n-butane, n-pentane, n-hexane, cyclohexane, heptane, octane, nonane, decane, adamantane and the like.
  • Examples of unsaturated hydrocarbons having 2 to 10 carbon atoms include ethene, ethyne, propene, propyne, 1-butene, 2-butene, 1,3-butadiene, 1-pentene, 2-pentene, 1,3- Pentadiene, 1-hexene, 3-hexene, 1,3,5-hexatriene, cyclohexene, 1-heptene, 1-octene, 3-octene, 1,3,5,7-octatetraene, 1-nonene, 1 -Decene and the like.
  • Examples of the aromatic hydrocarbon having 6 to 10 carbon atoms include benzene, phenol, methylbenzene, dimethylbenzene, ethylbenzene, butylbenzene, naphthalene, and the like.
  • n is preferably 2 to 4 and more preferably 2 because excellent cycle characteristics, high capacity can be obtained even after repeated charge and discharge use, and synthesis is easy.
  • R 4 of the compound represented by the general formula (1) is an n-valent hydrocarbon having 1 to 10 carbon atoms and containing at least one oxygen atom or sulfur atom
  • R 4 is an oxygen atom or sulfur.
  • R 4 is a divalent to tetravalent aliphatic hydrocarbon having 1 to 10 carbon atoms containing at least one oxygen atom or sulfur atom.
  • the following compound No. 4-1. 4-18 since the excellent cycle characteristics and high capacity can be obtained even after repeated charge / discharge use, the compound No. 4-1, compound no. 4-7, and compound no. 4-10 is preferred, and compound No. 4-1 and compound no. 4-7 is more preferable.
  • R 4 when R 4 is a heterocyclic compound having 2 to 10 carbon atoms containing at least one oxygen atom or sulfur atom, examples of the heterocyclic compound include: Oxolane, thiolane, furan, thiophene, oxane, thiane, pyran, benzofuran, benzothiophene, thienothiophene, dibenzofuran, dibenzothiophene and the like.
  • thiophene and furan are preferable, and thiophene is more preferable because excellent cycle characteristics and high capacity can be obtained even after repeated charge and discharge use.
  • R 4 is a heterocyclic compound having 2 to 10 carbon atoms, and n is 2, for example, the following compound No. 5-1 to No. 5 5-14.
  • the nonaqueous electrolyte used in the present invention contains at least one compound represented by the general formula (1).
  • a nonaqueous electrolyte secondary battery having a high electric capacity can be obtained even after repeated charge and discharge.
  • the content of the compound is preferably 0.01% by mass to 20% by mass in the nonaqueous electrolyte, more preferably 0.05% by mass to 10% by mass in the nonaqueous electrolyte, Most preferably, it is 0.1% by mass to 5% by mass in the electrolyte.
  • the non-aqueous electrolyte used in the present invention does not include a non-aqueous electrolyte obtained by dissolving a metal salt in an organic solvent, a polymer gel electrolyte in which the metal salt is dissolved in an organic solvent and gelled with a polymer, and does not contain an organic solvent. Any genuine polymer electrolyte in which a metal salt is dispersed in a polymer can be used.
  • the metal salt used for the non-aqueous electrolyte and the polymer gel electrolyte may be a conventionally known lithium salt such as LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (SO 2 F) 2 , LiC (CF 3 SO 2 ) 3 , LiB (CF 3 SO 3 ) 4 , LiB (C 2 O 4 ) 2 , LiBF 2 (C 2 O 4 ), LiSbF 6 , LiSiF 5 , LiSCN, LiClO 4 , LiCl, LiF, LiBr, LiI, LiAlF 4 , LiAlCl 4 , LiPO 2 F 2 , and derivatives thereof, among which LiPF 6
  • Examples of the metal salt used for the pure polymer electrolyte when the non-aqueous electrolyte secondary battery of the present invention is a lithium ion secondary battery include LiN (CF 3 SO 2 ) 2 and LiN (C 2 F 5 SO 2). ) 2 , LiN (SO 2 F) 2 , LiC (CF 3 SO 2 ) 3 , LiB (CF 3 SO 3 ) 4 , and LiB (C 2 O 4 ) 2 .
  • the lithium salt concentration in the non-aqueous electrolyte of a lithium ion secondary battery may be insufficient if the lithium salt concentration is too low. If the lithium salt concentration is too high, the stability of the non-aqueous electrolyte may be reduced. Since there is a risk of damage, 0.5 to 7 mol / L is preferable, and 0.8 to 1.8 mol / L is more preferable.
  • the lithium salt can be used in combination of two or more.
  • the metal salt used for the non-aqueous electrolyte and the polymer gel electrolyte is sodium obtained by replacing lithium in the lithium salt with sodium.
  • a salt can be used, and the sodium salt can be used at the same concentration as the lithium salt in the case of a lithium ion secondary battery.
  • Sodium salts can be used in combination of two or more.
  • the non-aqueous electrolyte of the present invention can further contain nitrate and nitrite in addition to the metal salt.
  • nitrates include lithium nitrate, sodium nitrate, potassium nitrate, cesium nitrate, barium nitrate, ammonium nitrate, manganese nitrate, zinc nitrate, and nickel nitrate.
  • the nitrite include lithium nitrite, sodium nitrite, potassium nitrite, cesium nitrite, ammonium nitrite, manganese nitrite, zinc nitrite, and nickel nitrite.
  • lithium nitrate and sodium nitrate are preferable because a high capacity can be obtained after the charge / discharge cycle.
  • concentration of nitrate and nitrite in the non-aqueous electrolyte is preferably 0.01% by mass to 10% by mass, and preferably 0.1% by mass to 5% by mass because a high capacity is obtained after the charge / discharge cycle. % Is more preferable.
  • organic solvent used in the non-aqueous electrolyte of the present invention an organic solvent usually used for a non-aqueous electrolyte of a non-aqueous electrolyte secondary battery can be used.
  • organic solvents that are usually used in nonaqueous electrolytes of nonaqueous electrolyte secondary batteries include saturated cyclic carbonate compounds, saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds, amide compounds, saturated chain carbonate compounds, and chain ethers. Examples thereof include a compound, a cyclic ether compound, and a saturated chain ester compound.
  • the organic solvent can be used alone or in combination of two or more.
  • saturated cyclic carbonate compounds saturated cyclic ester compounds, sulfoxide compounds, sulfone compounds, and amide compounds are preferable because they have a high relative dielectric constant and thus serve to increase the dielectric constant of the nonaqueous electrolyte.
  • a saturated cyclic carbonate compound is particularly preferable.
  • the saturated cyclic carbonate compound include ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,1-dimethylethylene carbonate, and the like. It is done.
  • saturated cyclic ester compound examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -hexanolactone, and ⁇ -octanolactone.
  • sulfoxide compound examples include dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, diphenyl sulfoxide, thiophene, and the like.
  • sulfone compound examples include dimethyl sulfone, diethyl sulfone, dipropyl sulfone, diphenyl sulfone, sulfolane (also referred to as tetramethylene sulfone), 3-methyl sulfolane, 3,4-dimethyl sulfolane, 3,4-diphenmethyl sulfolane. , Sulfolane, 3-methylsulfolene, 3-ethylsulfolene, 3-bromomethylsulfolene and the like, and sulfolane and tetramethylsulfolane are preferable.
  • the amide compound examples include N-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like.
  • saturated chain carbonate compounds, chain ether compounds, cyclic ether compounds and saturated chain ester compounds can reduce the viscosity of the nonaqueous electrolyte and increase the mobility of electrolyte ions. Battery characteristics such as output density can be made excellent. Moreover, since it is low-viscosity, the performance of the nonaqueous electrolyte at low temperatures can be enhanced.
  • a saturated chain carbonate compound is preferable.
  • saturated chain carbonate compound examples include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl butyl carbonate, methyl-t-butyl carbonate, diisopropyl carbonate, t-butyl propyl carbonate, and the like.
  • Examples of the chain ether compound or the cyclic ether compound include dimethoxyethane, ethoxymethoxyethane, diethoxyethane, tetrahydrofuran, dioxolane, dioxane, 1,2-bis (methoxycarbonyloxy) ethane, 1,2-bis ( Ethoxycarbonyloxy) ethane, 1,2-bis (ethoxycarbonyloxy) propane, ethylene glycol bis (trifluoroethyl) ether, propylene glycol bis (trifluoroethyl) ether, ethylene glycol bis (trifluoromethyl) ether, diethylene glycol bis (Trifluoroethyl) ether and the like can be mentioned, and among these, dioxolane is preferable.
  • saturated chain ester compound monoester compounds and diester compounds having a total number of carbon atoms in the molecule of 2 to 8 are preferable, and specific compounds include, for example, methyl formate, ethyl formate, methyl acetate, Ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, methyl isobutyrate, methyl trimethyl acetate, ethyl trimethyl acetate, methyl malonate, ethyl malonate, methyl succinate, ethyl succinate , Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethylene glycol diacetyl, propylene glycol diacetyl, etc., including methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate
  • acetonitrile, propionitrile, nitromethane, derivatives thereof, and various ionic liquids can be used as the organic solvent used for the preparation of the nonaqueous electrolytic solution.
  • Examples of the polymer used for the polymer gel electrolyte include polyethylene oxide, polypropylene oxide, polyvinyl chloride, polyacrylonitrile, polymethyl methacrylate, polyethylene, polyvinylidene fluoride, and polyhexafluoropropylene.
  • Examples of the polymer used in the pure polymer electrolyte include polyethylene oxide, polypropylene oxide, and polystyrene sulfonic acid.
  • the nonaqueous electrolyte used in the present invention may contain an azide, an organic nitro compound, a pyridine N-oxide compound, an alkylamine N-oxide compound or tetramethylpiperidine N-oxyl in order to increase the capacity after a charge / discharge cycle. is there.
  • Examples of the azide include hydrogen azide, lithium azide, sodium azide, lead azide, diphenyl phosphate azide and the like.
  • Examples of the organic nitro compound include nitromethane, nitropropane, nitrobutane, nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, nitropyridine, and dinitropyridine.
  • Examples of the pyridine N-oxide compound include pyridine N-oxide, 4- (dimethylamino) pyridine N-oxide, 2,6 dimethylpyridine N-oxide, and 2,6 dichloropyridine N-oxide.
  • alkylamine N-oxide compound examples include N, N-dimethyloctylamine N-oxide, N, N-dimethyldecylamine N-oxide, N, N-dodecylamine N-oxide, dimethyllaurylamine N-oxide, N, N-dimethylaniline N-oxide, N-methylmorpholine N-oxide and the like can be mentioned.
  • azides are preferred, and lithium azide and sodium azide are more preferred.
  • the concentration in the non-aqueous electrolyte of at least one compound selected from the group consisting of organic nitro compounds, azide compounds, and organic nitro compounds is too small to show the effect of addition.
  • 0.01% by mass to 10% by mass is preferable, and 0.1% by mass to 5% by mass is more preferable.
  • the nonaqueous electrolyte used in the present invention may further contain a compound represented by the general formula (2) in order to enhance storage stability.
  • R 5 to R 9 are each independently a hydrogen atom, a halogen atom, a nitrile group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or 5 carbon atoms
  • a cycloalkyl group having 12 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an oxyalkyl group having 1 to 12 carbon atoms, an acyl group having 1 to 12 carbon atoms, or —SiR R 12 represents a group represented by R 13 R 14
  • R 10 to R 14 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a group having 5 to 12 carbon atoms.
  • X 1 represents an m-valent alkyl group having 1 to 12 carbon atoms, 2 to 12 carbon atoms.
  • alkyl group having 1 to 12 carbon atoms examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, Examples include isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, and 2-methylhexyl group.
  • alkenyl group having 2 to 12 carbon atoms examples include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, 2- Butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, 2-methylvinyl, 1-methylallyl, 1,1-dimethylallyl, pentenyl, hexenyl, heptenyl, octenyl Group, nonenyl group, decenyl group, undecenyl group, dodecenyl group and the like.
  • Examples of the cycloalkyl group having 5 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a 2-norbornyl group.
  • Examples of the aryl group having 6 to 12 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a 2-norbornyl group.
  • Examples of the aryl group having 6 to 12 carbon atoms include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, and ethylphenyl groups.
  • Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, tolylmethyl group, tolylethyl group, tolylpropyl group, xylylmethyl group, xylylethyl group, xylylpropyl group and the like.
  • Examples of the oxyalkyl group having 1 to 12 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group and the like.
  • acyl group having 1 to 12 carbon atoms examples include methanoyl group, ethanoyl group, propanoyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, dodecanoyl group and the like. It is done.
  • R 5 to R 9 are preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom, from the viewpoint of easy availability of raw materials.
  • R 10 to R 14 are preferably a hydrogen atom, a methyl group, or an ethyl group, more preferably a methyl group, from the viewpoint of ease of synthesis.
  • the amount of the compound represented by the general formula (2) added to the non-aqueous electrolyte is preferably 0.1% by mass to 10% by mass, more preferably 0.1% by mass to 7.0% by mass, It is more preferably from 5% by mass to 7.0% by mass, and most preferably from 1% by mass to 5% by mass.
  • the content is less than 0.1% by mass, a sufficient effect cannot be exerted.
  • the content is more than 10% by mass, the increase effect corresponding to the addition amount is not seen, but the battery performance is reduced. There is.
  • the non-aqueous electrolyte may contain known additives such as an electrode film forming agent, an antioxidant, a flame retardant, and an overcharge preventing agent in order to improve battery life and safety.
  • additives such as an electrode film forming agent, an antioxidant, a flame retardant, and an overcharge preventing agent in order to improve battery life and safety.
  • concentration in the non-aqueous electrolyte is too small to exert the effect of addition, and when the concentration is too large, the characteristics of the non-aqueous electrolyte secondary battery may be adversely affected. 01% by mass to 10% by mass is preferable, and 0.1% by mass to 5% by mass is more preferable.
  • a separator between the positive electrode and the negative electrode.
  • a commonly used polymer microporous film can be used without particular limitation.
  • the film include polyethylene, polypropylene, polyvinylidene fluoride, polyvinylidene chloride, polyacrylonitrile, polyacrylamide, polytetrafluoroethylene, polysulfone, polyethersulfone, polycarbonate, polyamide, polyimide, polyethylene oxide and polypropylene oxide.
  • the microporosity method includes a phase separation method in which a polymer compound and a solvent solution are formed into a film while microphase separation is performed, and the solvent is extracted and removed to make it porous.
  • the film is extruded and then heat treated, the crystals are arranged in one direction, and a “stretching method” or the like is performed by forming a gap between the crystals by stretching, and is appropriately selected depending on the film used.
  • the shape of the nonaqueous electrolyte secondary battery of the present invention is not particularly limited, and can be various shapes such as a coin shape, a cylindrical shape, a square shape, and a laminate shape.
  • FIG. 1 shows an example of a coin-type battery of the nonaqueous electrolyte secondary battery of the present invention
  • FIGS. 2 and 3 show examples of a cylindrical battery, respectively.
  • 1 is a positive electrode capable of releasing lithium ions
  • 1a is a positive electrode current collector
  • 2 is a negative electrode capable of inserting and extracting lithium ions released from the positive electrode
  • 2a is A negative electrode current collector
  • 3 is a nonaqueous electrolyte
  • 4 is a positive electrode case made of stainless steel
  • 5 is a negative electrode case made of stainless steel
  • 6 is a gasket made of polypropylene
  • 7 is a separator made of polyethylene.
  • 11 is a negative electrode
  • 12 is a negative electrode current collector
  • 13 is a positive electrode
  • 14 is a positive electrode current collector
  • 15 is a nonaqueous electrolyte
  • 16 is a separator
  • 17 is a positive terminal
  • 18 is a negative terminal
  • 19 is a negative electrode plate
  • 20 is a negative electrode lead
  • 21 is a positive electrode plate
  • 22 is a positive electrode lead
  • 23 is a case
  • 24 is an insulating plate
  • 25 is a gasket
  • 26 is a safety valve 27 are PTC elements.
  • a laminate film or a metal container can be used as an exterior member of the nonaqueous electrolyte secondary battery of the present invention.
  • the thickness of the exterior member is usually 0.5 mm or less, preferably 0.5 mm or less.
  • Examples of the shape of the exterior member include a flat type (thin type), a square type, a cylindrical type, a coin type, and a button type.
  • a multilayer film having a metal layer between resin films can also be used.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
  • a polymer material such as polypropylene, polyethylene, nylon, or polyethylene terephthalate can be used.
  • the laminate film can be formed into the shape of an exterior member by performing heat sealing.
  • the metal container can be formed of, for example, stainless steel, aluminum, aluminum alloy, or the like.
  • the aluminum alloy an alloy containing elements such as magnesium, zinc, and silicon is preferable.
  • transition metals such as iron, copper, nickel, and chromium
  • the product was placed in a glass tube oven and heated at 250 ° C. for 3 hours with vacuum suction to remove elemental sulfur.
  • the obtained sulfur-modified product was pulverized using a ball mill and classified with a sieve to obtain sulfur-modified polyacrylonitrile having an average particle size of 10 ⁇ m.
  • the sulfur content was 38.4% by mass.
  • Sulfur-modified pitch compound (A-2) 100 parts by weight of coal pitch (coal tar, manufactured by Yoshida Refinery) and 500 parts by weight of elemental sulfur (manufactured by Sigma Aldrich, average particle size 200 ⁇ m) are used as the pitch compound, in accordance with Example 1 of JP2012-099342A
  • the reaction was carried out to obtain a reaction product.
  • the obtained reaction product was pulverized to obtain sulfur-modified pitch compound A-2 having an average particle size of 15 ⁇ m.
  • the sulfur content was 32.5% by mass.
  • Sulfur-modified polynuclear aromatic compound (A-3) 100 parts by mass of anthracene (manufactured by Tokyo Chemical Industry) and 500 parts by mass of elemental sulfur (manufactured by Sigma-Aldrich, average particle diameter 200 ⁇ m) are used as the sulfur-modified polynuclear aromatic ring compound, and in accordance with Reference Example 1 of JP2012-150934A Reaction was performed to obtain a reaction product.
  • the obtained reaction product was pulverized to obtain a sulfur-modified polynuclear aromatic compound A-3 having an average particle size of 16 ⁇ m.
  • the sulfur content was 47.7% by mass.
  • A-1 sulfur-modified polyacrylonitrile
  • the electrode mixture paste was applied to a current collector made of carbon-coated aluminum foil (thickness: 22 ⁇ m) by a doctor blade method, and allowed to stand at 90 ° C. for 3 hours to dry. Thereafter, this electrode was cut into a predetermined size (disc shape), and further vacuum-dried at 150 ° C. for 2 hours immediately before use to produce a positive electrode.
  • a current collector made of carbon-coated aluminum foil (thickness: 22 ⁇ m) by a doctor blade method, and allowed to stand at 90 ° C. for 3 hours to dry. Thereafter, this electrode was cut into a predetermined size (disc shape), and further vacuum-dried at 150 ° C. for 2 hours immediately before use to produce a positive electrode.
  • LiPF 6 was dissolved at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate to prepare an electrolyte solution. This is followed by compound no.
  • Example 2 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 2 was produced in the same manner as in Example 1, except that 4% by mass of 4-7 was added.
  • Example 3 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no. Compound No. 5-4 in which the substitution positions are ⁇ and ⁇ ′ positions on the thiophene ring. A nonaqueous electrolyte secondary battery of Example 3 was produced in the same manner as in Example 1 except that 1.0% by mass of 5-4A was added.
  • Example 4 A nonaqueous electrolyte secondary battery of Example 4 was produced in the same manner as in Example 1, except that 0.1% by mass of lithium nitrate was further added to the nonaqueous electrolyte of Example 1.
  • Example 5 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no.
  • a nonaqueous electrolyte secondary battery of Example 5 was produced in the same manner as in Example 1 except that 1.0% by mass of 4-7 and 0.1% by mass of lithium nitrate were added.
  • Example 6 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of compound 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 6 was produced in the same manner as in Example 1, except that 1.0% by mass of 5-4A and 0.1% by mass of lithium nitrate were added.
  • Example 7 The same procedure as in Example 1 was performed except that the sulfur-modified pitch compound (A-2) was used instead of the sulfur-modified polyacrylonitrile (A-1) as the positive electrode active material in Example 1. A water electrolyte secondary battery was produced.
  • Example 8 was carried out in the same manner as in Example 1, except that the sulfur-modified polynuclear aromatic compound (A-3) was used instead of sulfur-modified polyacrylonitrile (A-1) as the positive electrode active material of Example 1.
  • a non-aqueous electrolyte secondary battery was prepared.
  • Example 9 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 9 was produced in the same manner as in Example 1, except that 0.5% by mass of 2-1 and 0.5% by mass of compound 6-1 were added.
  • Example 10 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no.
  • a nonaqueous electrolyte secondary battery of Example 10 was produced in the same manner as in Example 1, except that 0.5% by mass of 4-7 and 0.5% by mass of Compound 6-1 were added.
  • Example 11 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no.
  • a nonaqueous electrolyte secondary battery of Example 11 was produced in the same manner as in Example 1, except that 0.5% by mass of 2-1 and 0.5% by mass of vinylene carbonate (VC) were added.
  • VC vinylene carbonate
  • Example 12 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no.
  • a nonaqueous electrolyte secondary battery of Example 12 was produced in the same manner as in Example 1, except that 0.5% by mass of 4-7 and 0.5% by mass of vinylene carbonate (VC) were added.
  • VC vinylene carbonate
  • Example 13 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no.
  • a nonaqueous electrolyte secondary battery of Example 13 was produced in the same manner as in Example 1 except that 0.5% by mass of 2-1 and 0.5% by mass of fluoroethylene carbonate (FEC) were added.
  • FEC fluoroethylene carbonate
  • Example 14 Compound No. 1 was added to the non-aqueous electrolyte of Example 1. Instead of adding 1.0% by mass of 2-1, compound no.
  • a nonaqueous electrolyte secondary battery of Example 14 was produced in the same manner as in Example 1, except that 0.5% by mass of 4-7 and 0.5% by mass of fluoroethylene carbonate (FEC) were added.
  • FEC fluoroethylene carbonate
  • Example 15 Instead of using an electrolyte solution prepared by dissolving LiPF 6 at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate in the nonaqueous electrolyte of Example 1, 1,3- Except for using an electrolyte solution in which lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) was dissolved at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of dioxolane and 50% by volume of 1,2-dimethoxyethane, A nonaqueous electrolyte secondary battery of Example 15 was produced in the same manner as in Example 1.
  • LiTFSI lithium bis (trifluoromethanesulfonyl) imide
  • Example 16> To the non-aqueous electrolyte of Example 15, compound No. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 16 was produced in the same manner as in Example 15, except that 1.0% by mass of 4-7 was added.
  • Example 17 To the non-aqueous electrolyte of Example 15, compound No. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 17 was produced in the same manner as in Example 15 except that 1.0% by mass of 5-4A was added.
  • Example 18 A nonaqueous electrolyte secondary battery of Example 18 was produced in the same manner as in Example 15, except that 0.1% by mass of lithium nitrate was further added to the nonaqueous electrolyte of Example 15.
  • Example 19 A nonaqueous electrolyte secondary battery of Example 19 was produced in the same manner as in Example 15, except that 0.1% by mass of lithium nitrate was further added to the nonaqueous electrolyte of Example 16.
  • Example 20 A nonaqueous electrolyte secondary battery of Example 20 was produced in the same manner as in Example 15, except that 0.1% by mass of lithium nitrate was further added to the nonaqueous electrolyte of Example 17.
  • Example 21 To the non-aqueous electrolyte of Example 15, compound No. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 21 was produced in the same manner as in Example 15, except that 0.5% by mass of 2-1 and 0.5% by mass of vinylene carbonate were added.
  • Example 22 To the non-aqueous electrolyte of Example 15, compound No. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 22 was produced in the same manner as in Example 15, except that 0.5% by mass of 4-7 and 0.5% by mass of vinylene carbonate were added.
  • Example 23 To the non-aqueous electrolyte of Example 15, compound No. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 23 was produced in the same manner as in Example 15, except that 2-1 was added by 0.5 mass% and fluoroethylene carbonate was added by 0.5 mass%.
  • Example 24 To the non-aqueous electrolyte of Example 15, compound No. Instead of adding 1.0% by mass of 2-1, compound no. A nonaqueous electrolyte secondary battery of Example 24 was produced in the same manner as in Example 15, except that 0.5% by mass of 4-7 and 0.5% by mass of fluoroethylene carbonate were added.
  • Example 25> Instead of using an electrolyte solution in which LiPF 6 was dissolved at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate in the nonaqueous electrolyte of Example 7, 1,3- Except for using an electrolyte solution in which lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) was dissolved at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of dioxolane and 50% by volume of 1,2-dimethoxyethane, A nonaqueous electrolyte secondary battery of Example 26 was produced in the same manner as in Example 7.
  • LiPF 6 lithium bis (trifluoromethanesulfonyl) imide
  • Example 26> Instead of using an electrolyte solution in which LiPF 6 was dissolved at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of ethylene carbonate and 50% by volume of diethyl carbonate in the nonaqueous electrolyte of Example 8, 1,3- Except for using an electrolyte solution in which lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) was dissolved at a concentration of 1.0 mol / L in a mixed solvent composed of 50% by volume of dioxolane and 50% by volume of 1,2-dimethoxyethane, A nonaqueous electrolyte secondary battery of Example 26 was produced in the same manner as in Example 7.
  • LiPF 6 lithium bis (trifluoromethanesulfonyl) imide
  • Compound No. 1 was added to the non-aqueous electrolyte of Example 1.
  • a nonaqueous electrolyte secondary battery of Comparative Example 4 was produced in the same manner as in Example 1, except that 1.0% by mass of vinylene carbonate (VC) was added instead of adding 1.0% by mass of 2-1. .
  • VC vinylene carbonate
  • Compound No. 1 was added to the non-aqueous electrolyte of Example 1.
  • a nonaqueous electrolyte secondary battery of Comparative Example 3 was produced in the same manner as in Example 1, except that 0.1% by mass of lithium nitrate was added instead of adding 1.0% by mass of 2-1.
  • Example 6 Compound No. 1 was added to the non-aqueous electrolyte of Example 1.
  • a nonaqueous electrolyte secondary battery of Comparative Example 6 was produced in the same manner as in Example 1, except that 1.0% by mass of fluoroethylene carbonate was added instead of adding 1.0% by mass of 2-1.
  • ⁇ Battery evaluation 1> The nonaqueous electrolyte secondary batteries of Examples 1 to 8 and Comparative Examples 1 to 5 were placed in a constant temperature bath at 25 ° C., the charge end voltage was 3.0 V, the discharge end voltage was 1.0 V, and the charge rate was 0.1 C. The charge / discharge test at a discharge rate of 0.1 C was performed for 5 cycles. Thereafter, the sample was placed in a thermostatic chamber at ⁇ 10 ° C., a charge / discharge test of 100 cycles was performed at a charge rate of 0.3 C and a discharge rate of 0.3 C, and the discharge capacity was measured. This discharge capacity was set to L1. The unit is mAh / g, and the results are shown in Table 1.
  • ⁇ Battery evaluation 2> The nonaqueous electrolyte secondary batteries of Examples 1 to 8 and Comparative Examples 1 to 5 were placed in a constant temperature bath at 25 ° C., the charge end voltage was 3.0 V, the discharge end voltage was 1.0 V, and the charge rate was 0.1 C. Then, a charge / discharge test at a discharge rate of 0.1 C was performed for 5 cycles, followed by a charge / discharge test of 150 cycles at a charge rate of 1.0 C and a discharge rate of 1.0 C to measure the discharge capacity. This discharge capacity was set to L2. The unit is mAh / g, and the results are shown in Table 1.
  • ⁇ Battery evaluation 3> The nonaqueous electrolyte secondary batteries of Examples 1 to 8 and Comparative Examples 1 to 5 were placed in a constant temperature bath at 25 ° C., the charge end voltage was 3.0 V, the discharge end voltage was 1.0 V, and the charge rate was 0.1 C. Then, a charge / discharge test at a discharge rate of 0.1 C was performed for 5 cycles, and then a charge test at a charge rate of 0.1 C was performed once. Then, it put into a 45 degreeC thermostat and preserve
  • a positive electrode having a sulfur-modified organic compound a negative electrode having a metal selected from the group consisting of alkali metals and alkaline earth metals, at least one of the general formula (1), and an alkali metal
  • the nonaqueous electrolyte secondary battery of the present invention comprising a nonaqueous electrolyte containing at least one metal salt selected from the group consisting of a salt or an alkaline earth metal salt is after 150 cycles compared to the secondary battery shown in the comparative example. The capacity of was large.
  • the nonaqueous electrolyte secondary battery of the present invention has both excellent charge / discharge characteristics at low temperatures and excellent high-temperature storage stability.
  • non-aqueous electrolyte secondary battery having a high capacity even after repeated charging and discharging.
  • nonaqueous electrolyte secondary battery that is excellent in capacity characteristics after storage at high temperatures.

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Abstract

La présente invention aborde le problème de la fourniture d'une batterie secondaire à électrolyte non aqueux ayant une grande capacité même après charge et décharge répétées. La présente invention concerne une batterie secondaire à électrolyte non aqueux qui comprend : une électrode positive qui contient un composé organique modifié par du soufre ; une électrode négative qui contient au moins un métal choisi dans le groupe constitué par un métal alcalin et un métal alcalino-terreux ; et un électrolyte non aqueux qui contient au moins un composé représenté par la formule générale (1) et au moins un sel métallique choisi dans le groupe constitué par un sel de métal alcalin et un sel de métal alcalino-terreux. (Dans la formule, R1 à R3 sont chacun indépendamment un groupe hydrocarboné ayant 1 à 10 atomes de carbone, R4 représente un groupe hydrocarboné de valence n ayant 1 à 10 atomes de carbone ou un groupe hydrocarboné de valence n ayant 1 à 10 atomes de carbone qui comprend au moins un atome d'oxygène ou un atome de soufre, et n est un nombre entier de 1 à 6.)
PCT/JP2019/015021 2018-04-25 2019-04-04 Batterie secondaire à électrolyte non aqueux WO2019208153A1 (fr)

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CN114207902A (zh) * 2020-04-14 2022-03-18 株式会社Lg新能源 锂硫电池用电解质及包含其的锂硫电池
JP2022553728A (ja) * 2020-04-17 2022-12-26 エルジー エナジー ソリューション リミテッド リチウム二次電池用電解液及びこれを含むリチウム二次電池
EP4099468A4 (fr) * 2020-01-30 2024-01-10 Panasonic Ip Man Co Ltd Additif pour électrolyte non aqueux, électrolyte non aqueux contenant celui-ci, et batterie secondaire à électrolyte non aqueux

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CN114207902A (zh) * 2020-04-14 2022-03-18 株式会社Lg新能源 锂硫电池用电解质及包含其的锂硫电池
JP2022542350A (ja) * 2020-04-14 2022-10-03 エルジー エナジー ソリューション リミテッド リチウム－硫黄電池用電解質及びこれを含むリチウム－硫黄電池
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CN112670575A (zh) * 2020-12-22 2021-04-16 上海卡耐新能源有限公司 一种锂离子电池电解液用添加剂及其应用

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